HCFO-containing isocyanate-reactive compositions, related foam-forming compositions and PUR-PIR foams

ABSTRACT

Disclosed are HCFO-containing isocyanate-reactive compositions, foam-forming compositions containing such isocyanate-reactive compositions, rigid PUR-PIR foams made using such foam-forming compositions, and methods for producing such foams, including use of such foams as insulation in discontinuous foam panel applications. The isocyanate-reactive composition can exhibit a long shelf life, be shelf-stable, and produce a foam with good physical properties.

FIELD

This specification pertains generally to hydrochlorofluoroolefin(“HCFO”)-containing isocyanate-reactive compositions, foam-formingcompositions containing such isocyanate-reactive compositions, rigidfoams made using such foam-forming compositions, and methods forproducing such foams, including use of such foams as panel insulation.

BACKGROUND

Flame-retardant rigid polyurethane foams are used in numerousindustries. They are produced by reacting an appropriate polyisocyanateand an isocyanate-reactive compound, usually a polyol, in the presenceof a blowing agent and catalysts to produce polyisocyanurate-containingand polyurethane-containing foams. One use of such foams is as a thermalinsulation medium in the construction of panel assemblies, such asdoors, including garage doors. The thermal insulating properties ofclosed-cell rigid foams are dependent upon a number of factors,including the average cell size and the thermal conductivity of thecontents of the cells.

Chlorofluorocarbons (CFC's) and hydrogen-containing chlorofluorocarbons(HCFC's) have been used as blowing agents to produce these foams becauseof their exceptionally low vapor thermal conductivity. However, theirozone-depletion potential is a drawback to their use. Alternativeblowing agents, such as hydrofluorocarbons (HFC's) are also used, butthey are greenhouse gases. Hydrocarbons, such as pentane isomers, havealso been used, but these are flammable and have lower energyefficiency. Halogenated hydroolefinic compounds, such as HCFOs, are nowpossible candidates as replacements for HFCs, since their chemicalinstability in the lower atmosphere provides for a low global warmingpotential and zero or near zero ozone depletion properties.

Formulations used to produce thermally insulating rigid polyurethanefoam, particularly those used in the construction of panel assemblies,utilize catalysts to control the relative rates of water-polyisocyanate(gas-forming or blowing), the polyol-polyisocyanate (gelling) reactionto form polyurethane (“PUR”), and the isocyanate-isocyanatetrimerization reaction to form polyisocyanurate (“PIR”). In the gellingreaction, the isocyanate reacts with polyols to form the polyurethanefoam matrix. In the trimerization reaction, isocyanates react with oneanother to form macromolecules with isocyanurate structures(polyisocyanurates). In the blowing reaction, the isocyanate reacts withwater in the formulation to form polyurea and carbon dioxide. Whilethese reactions take place at different rates, it is necessary toproperly balance them to produce high-quality foam. For example, if theblowing reaction occurs faster than the gelling reaction, the gasgenerated by the reaction may expand before the polyurethane matrix isstrong enough to contain it and foam collapse can occur. In contrast, ifthe gelling reaction occurs faster than the blowing reaction, the foamcells will remain closed, causing the foam to shrink as it cools.Moreover, if the gelling reaction occurs while the reaction mixture isstill flowing, cell stretching may occur, resulting in elongated cellstructures. Foams with such elongated cell structures generally exhibitpoorer physical properties, such as poorer compressive strength, poorerdimensional stability (more foam shrinkage), poorer thermal insulationproperties, and poorer foam quality (due to surface voids and otherdefects).

As a result, to achieve the proper balance, formulations often utilize acombination of blow catalysts, gel catalysts, and/or trimerizationcatalysts Amine catalysts, for example, are known to have a greatereffect on the water-polyisocyanate blowing reaction, whereas organotincatalysts are known to have a greater effect on thepolyol-polyisocyanate gelling reaction.

A drawback to at least some HCFOs as blowing agents in the production ofsatisfactory isocyanate-based foams is poor shelf-life. Blowing agentsoften are combined with polyols and other components, such assurfactant(s) and the catalyst(s), to form a so-called “B-side” pre-mixthat may be stored for up to several months prior to being combined withan “A-side” isocyanate component to form the foam.

With certain HCFOs, however, if the B-side composition is aged prior tocombining with the polyisocyanate, the foam can be of lower quality andmay even collapse during the formation of foam. The poor foam structureis thought to be attributable to the reaction of certain catalysts,particularly amine catalysts, with these HCFOs which results in thepartial decomposition of the blowing agent and, as a result, undesirablemodification of silicone surfactants, resulting in poor foam structureand quality.

To combat this issue, certain amine catalysts have been identified thatcan exhibit substantially improved stability with HCFOs. These includemorpholines and imidazoles. Such catalysts, however, are not withoutsome drawbacks. In addition to being relatively costly, they tend to beweak catalysts, thereby necessitating their use in relatively highloadings, which both amplifies the cost impact and limits the ability ofa foam formulator to optimize the foam flow profile and quality. As aresult, it would be desirable to identify ways to reduce the amount ofsuch amine catalysts that are required in a formulation.

Foam-forming compositions used in the production of panel assemblies,particularly those produced in a discontinuous open and closed pourprocesses must exhibit a stringent combination of properties. Forexample, in addition to good thermal insulation properties, they mustexhibit target cream and gel times conducive to the manufacturingequipment and process that is used, and they must exhibit a long shelflife, which means that this gel time cannot change by a large amountafter storage of the foam-forming composition components for a longperiod of time (several months or more), even when a chemical blowingagent, such as water, is also used. The isocyanate-reactive compositionused must also be phase stable in that it does do not exhibit anysignificant phase separation over time. The foams also must exhibit gooddimensional stability (low foam shrinkage) even when the free-rise foamshave a relatively low density of less than 2.0 lb/ft³.

A composition that can fulfill most, if not all, of these requirements,while utilizing a HCFO blowing agent would, therefore, before highlydesirable.

SUMMARY

In certain respects, the present disclosure is directed toisocyanate-reactive compositions. These compositions comprise: (a) apolyol blend, (b) a blowing agent composition, and (c) a tertiary aminecatalyst. The polyol blend comprises: (1) a saccharide-initiatedpolyether polyol having an OH number of from 200 to 600 mg KOH/g and afunctionality of 4 to 6; (2) an aromatic polyester polyol having an OHnumber of 150 to 410 mg KOH/g and a functionality of 1.5 to 3; and (3)an alkanolamine-initiated polyether polyol having an OH number of atleast 500 mg KOH/g and a functionality of 2.5 to 4. The blowing agentcomposition comprises a physical blowing agent comprising ahydrochlorofluoroolefin and a carbon dioxide generating chemical blowingagent.

The present specification is also directed to foam-forming compositionsthat include such isocyanate-reactive compositions, rigid PUR-PIR foamsproduced from such foam-forming compositions, methods for making suchrigid foams, and composite articles comprising such rigid foams, andpanel insulation that includes such rigid foams.

DETAILED DESCRIPTION

Various implementations are described and illustrated in thisspecification to provide an overall understanding of the structure,function, properties, and use of the disclosed inventions. It isunderstood that the various implementations described and illustrated inthis specification are non-limiting and non-exhaustive. Thus, theinvention is not limited by the description of the various non-limitingand non-exhaustive implementations disclosed in this specification. Thefeatures and characteristics described in connection with variousimplementations may be combined with the features and characteristics ofother implementations. Such modifications and variations are intended tobe included within the scope of this specification. As such, the claimsmay be amended to recite any features or characteristics expressly orinherently described in, or otherwise expressly or inherently supportedby, this specification. Further, Applicant(s) reserve the right to amendthe claims to affirmatively disclaim features or characteristics thatmay be present in the prior art. Therefore, any such amendments complywith the requirements of 35 U.S.C. § 112 and 35 U.S.C. § 132(a). Thevarious implementations disclosed and described in this specificationcan comprise, consist of, or consist essentially of the features andcharacteristics as variously described herein.

Any patent, publication, or other disclosure material identified hereinis incorporated by reference into this specification in its entiretyunless otherwise indicated, but only to the extent that the incorporatedmaterial does not conflict with existing definitions, statements, orother disclosure material expressly set forth in this specification. Assuch, and to the extent necessary, the express disclosure as set forthin this specification supersedes any conflicting material incorporatedby reference herein. Any material, or portion thereof, that is said tobe incorporated by reference into this specification, but whichconflicts with existing definitions, statements, or other disclosurematerial set forth herein, is only incorporated to the extent that noconflict arises between that incorporated material and the existingdisclosure material. Applicant(s) reserves the right to amend thisspecification to expressly recite any subject matter, or portionthereof, incorporated by reference herein.

In this specification, other than where otherwise indicated, allnumerical parameters are to be understood as being prefaced and modifiedin all instances by the term “about”, in which the numerical parameterspossess the inherent variability characteristic of the underlyingmeasurement techniques used to determine the numerical value of theparameter. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter described in the present description should atleast be construed in light of the number of reported significant digitsand by applying ordinary rounding techniques.

Also, any numerical range recited in this specification is intended toinclude all sub-ranges of the same numerical precision subsumed withinthe recited range. For example, a range of “1.0 to 10.0” is intended toinclude all sub-ranges between (and including) the recited minimum valueof 1.0 and the recited maximum value of 10.0, that is, having a minimumvalue equal to or greater than 1.0 and a maximum value equal to or lessthan 10.0, such as, for example, 2.4 to 7.6. Any maximum numericallimitation recited in this specification is intended to include alllower numerical limitations subsumed therein and any minimum numericallimitation recited in this specification is intended to include allhigher numerical limitations subsumed therein. Accordingly, Applicant(s)reserves the right to amend this specification, including the claims, toexpressly recite any sub-range subsumed within the ranges expresslyrecited herein. All such ranges are intended to be inherently describedin this specification such that amending to expressly recite any suchsub-ranges would comply with the requirements of 35 U.S.C. § 112 and 35U.S.C. § 132(a).

The grammatical articles “one”, “a”, “an”, and “the”, as used in thisspecification, are intended to include “at least one” or “one or more”,unless otherwise indicated. Thus, the articles are used in thisspecification to refer to one or more than one (i.e., to “at least one”)of the grammatical objects of the article. By way of example, “acomponent” means one or more components, and thus, possibly, more thanone component is contemplated and may be employed or used in animplementation of the described implementations. Further, the use of asingular noun includes the plural, and the use of a plural noun includesthe singular, unless the context of the usage requires otherwise.

As used herein, the term “functionality” refers to the average number ofreactive hydroxyl groups, —OH, present per molecule of the —OHfunctional material that is being described. In the production ofpolyurethane foams, the hydroxyl groups react with isocyanate groups,—NCO, that are attached to the isocyanate compound. The term “hydroxylnumber” refers to the number of reactive hydroxyl groups available forreaction, and is expressed as the number of milligrams of potassiumhydroxide equivalent to the hydroxyl content of one gram of the polyol(ASTM D4274-16). The term “equivalent weight” refers to the weight of acompound divided by its valence. For a polyol, the equivalent weight isthe weight of the polyol that will combine with an isocyanate group, andmay be calculated by dividing the molecular weight of the polyol by itsfunctionality. The equivalent weight of a polyol may also be calculatedby dividing 56,100 by the hydroxyl number of the polyol−EquivalentWeight (g/eq)=(56.1×1000)/OH number.

As indicated, certain implementations of the present specificationrelate to isocyanate-reactive compositions useful in the production ofrigid foams. A rigid foam is characterized as having a ratio ofcompressive strength to tensile strength of at least 0.5:1, elongationof less than 10%, as well as a low recovery rate from distortion and alow elastic limit, as described in “Polyurethanes: Chemistry andTechnology, Part II Technology,” J. H. Saunders & K. C. Frisch,Interscience Publishers, 1964, page 239.

The rigid foams of this specification are the reaction product of apolyurethane-foam forming composition that includes: (a) a diisocyanateand/or polyisocyanate; and (b) an isocyanate-reactive composition.

Any of the known organic isocyanates, modified isocyanates orisocyanate-terminated prepolymers made from any of the known organicisocyanates may be used. Suitable organic isocyanates include aromatic,aliphatic, and cycloaliphatic polyisocyanates and combinations thereof.Useful isocyanates include: diisocyanates such as m-phenylenediisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate,2,6-toluene diisocyanate, 1,6-hexamethylene diisocyanate,1,4-hexamethylene diisocyanate, 1,3-cyclohexane diisocyanate,1,4-cyclo-hexane diisocyanate, isomers of hexahydro-toluenediisocyanate, isophorone diisocyanate, dicyclo-hexylmethanediisocyanates, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethanediisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-biphenylenediisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate and3,3′-dimethyl-diphenyl-propane-4,4′-diisocyanate; triisocyanates such as2,4,6-toluene triisocyanate; and polyisocyanates such as4,4′-dimethyl-diphenylmethane-2,2′,5,5′-tetraisocyanate and thepolymethylene polyphenyl-polyisocyanates.

Undistilled or crude polyisocyanates may also be used. The crude toluenediisocyanate obtained by phosgenating a mixture of toluene diamines andthe crude diphenylmethane diisocyanate obtained by phosgenating crudediphenylmethanediamine (polymeric MDI) are examples of suitable crudepolyisocyanates. Suitable undistilled or crude polyisocyanates aredisclosed in U.S. Pat. No. 3,215,652.

Modified isocyanates are obtained by chemical reaction of diisocyanatesand/or polyisocyanates. Useful modified isocyanates include, but are notlimited to, those containing ester groups, urea groups, biuret groups,allophanate groups, carbodiimide groups, isocyanurate groups, uretdionegroups and/or urethane groups. Examples of modified isocyanates includeprepolymers containing NCO groups and having an NCO content of from 25to 35 weight percent, such as from 29 to 34 weight percent, such asthose based on polyether polyols or polyester polyols anddiphenylmethane diisocyanate.

In certain implementations, the polyisocyanate comprises amethylene-bridged polyphenyl polyisocyanate and/or a prepolymer ofmethylene-bridged polyphenyl polyisocyanates having an averagefunctionality of from 1.8 to 3.5, such as from 2.0 to 3.1, isocyanatemoieties per molecule and an NCO content of from 25 to 32 weightpercent, due to their ability to cross-link the polyurethane.

The isocyanate-reactive compositions described in this specificationcomprise a polyol blend. The polyol blend comprises asaccharide-initiated polyether polyol. As used herein,“saccharide-initiated polyether polyol” refers to a polyether polyolprepared by reacting at least one alkylene oxide with one or moresuitable starter compounds in the presence of a suitable catalyst, inwhich the starter compounds comprise one or more saccharide initiators.Examples of suitable alkylene oxides include ethylene oxide, propyleneoxide, butylene oxide, styrene oxide, epichlorohydrin, or a mixture ofany two or more thereof. Some examples of suitable saccharide initiatorsare sucrose, sorbitol, maltitol, etc. as well as other mono-saccharides,di-saccharides, tri-saccharides and polysaccharides. Other initiatorcompounds are often used in combination with the saccharide initiator toprepare the saccharide initiated polyether polyol. Saccharides can beco-initiated with for example, compounds such as water, propyleneglycol, glycerin, ethylene glycol, ethanol amines, diethylene glycol, ora mixture of any two or more thereof. As will be appreciated, it ispossible to use a wide variety of individual initiator compounds incombination with one another in which the functionality of theindividual initiator compounds does not fall within the functionalitiesset forth herein, provided that the average functionality of the mixtureof initiator compounds satisfies the overall functionality rangedisclosed herein.

Some examples of suitable catalysts which can be used include basiccatalysts (such as sodium or potassium hydroxide or tertiary amines suchas methyl imidazole) and double metal cyanide (DMC) catalysts.

In some implementations, the saccharide, such as sucrose, is firstreacted with ethylene oxide and then propylene oxide. In some cases, theethylene oxide is used in an amount of 10 to 50%, such as from 20 to40%, by weight of the total alkylene oxide used and the propylene oxideis used in an amount of from 50 to 90%, such as 60 to 80%, by weight ofthe total alkylene oxide used. In some implementations, the total amountof alkylene oxide used is selected so that the product has an averagemolecular weight of 300 to 1600 Da, such as 440 to 1000 Da.

In some implementations, the saccharide initiated polyether polyol hasan OH number of from 200 to 600 mg KOH/g, such as 300 to 550 mg KOH/g,such as 400 to 500 mg KOH/g, or, in some cases, 450 to 500 mg KOH/g, anda functionality of 4 to 6, such as 5 to 6, 5.2 to 5.8, or 5.4 to 5.6.

In some implementations, the saccharide-initiated polyether polyol isutilized in an amount of 10 to 45% by weight, such as 10 to 30% byweight, r, in some cases, 15 to 25% by weight, based on the total weightof the polyol blend.

The polyol blend further comprises an aromatic polyester polyol.Suitable aromatic polyester polyols include, for example, the reactionproduct of an aromatic diacid or anhydride with a suitable glycol ortriol. For example, polyester polyols can be the reaction product of aglycol and/or triol, such as ethylene glycol, propylene glycol, butyleneglycol, 1,3-butanediol, neopentyl glycol, diethylene glycol, dipropyleneglycol, triethylene glycol, tripropylene glycol, glycerol,trimethylolethane, trimethyolpropane, pentanediol, hexanediol,heptanediol, 1,3- and 1,4-dimethylol cyclohexane, or a mixture of anytwo or more thereof with an aromatic diacid or aromatic anhydride, suchas, for example, phthalic acid, isophthalic acid, terephthalic acid,phthalic anhydride, or a mixture of any two or more thereof. Some ofexamples of the suitable aromatic polyester polyols include thosecompounds which are available from Stepan Chemical under the Stepanpoltrade name such as, for example, Stepanpol® PS 3024 and Stepanpol PS2502A or from Invista under the Terate trade name, such as Terate®HT-5100 and HT-5500, or from Coim under the Isoexter trade name such asIsoexter® TB-265.

In certain implementations, the aromatic polyester polyol has an OHnumber of 150 to 410 mg KOH/g, such as 150 to 360 mg KOH/g, such as 200to 335 mg KOH/g, or, in some cases, 200 to 250 mg KOH/g, and afunctionality of 1.5 to 3, such as 1.9 to 2.5.

In some implementations, the aromatic polyester polyol is utilized in anamount of 50 to 85%, such as 60 to 80% by weight, based upon the totalweight of the polyol blend.

In certain implementations, the aromatic polyester polyol and thesaccharide-initiated polyether polyol are present in the polyol blend ina weight ratio of at least 2:1, such as 2:1 to 8:1, or, in some cases2:1 to 6:1 or 3:1 to 4:1.

The polyol blend further comprises an alkanolamine-initiated polyetherpolyol. As used herein, “alkanolamine-initiated polyether polyol” refersto a polyether polyol prepared by reacting at least one alkylene oxidewith one or more suitable starter compounds in the presence of asuitable catalyst, in which the starter compounds comprise one or morealkanolamines. Suitable catalysts including basic catalysts (such assodium or potassium hydroxide or tertiary amines such as methylimidazole) and DMC catalysts.

As used herein, the term “alkanolamine” refers to compounds representedby the formula:NH₂—Z—OHin which Z represents a divalent radical which is a straight chain orbranched chain alkylene radical having 2 to 6 carbon atoms, acycloalkylene radical having 4 to 6 carbon atoms or a dialkylene etherradical having 4 to 6 carbon atoms. The dialkylene ether radical may berepresented by the formula:—R—O—R—where each R represents a hydrocarbon radical having 2 to 3 carbonatoms.

Specific examples of suitable alkanolamines that may be used in thepreparation of the alkanolamine-initiated polyether polyol includemonoethanolamine, 1-amino-2-propanol, 2-amino-1-propanol,3-amino-1-propanol, 1-(2-aminoethoxy) ethanol, 1-amino-2-butanol,2-amino-3-butanol, 2-amino-2-methylpropanol, 5-amino pentanol,3-amino-2, 2-dimethyl propanol, 4-aminocyclohexanol, as well as mixturesof any two or more thereof.

To prepare the alkanolamine-initiated polyether polyol, the alkanolamineis reacted with an alkylene oxide. Suitable alkylene oxides includeethylene oxide, propylene oxide, butylene oxide, styrene oxide, andepichlorohydrin, as well as mixtures of any two or more thereof.

In some implementations, the alkanolamine-initiated polyether polyol hasan OH number of at least 500 mg KOH/g, such as 500 to 900 mg KOH/g, suchas 600 to 800 mg KOH/g, or, in some cases, 680 to 720 mg KOH/g, and afunctionality of 2.5 to 4, such as 2.5 to 3.5.

In some implementations, the alkanolamine-initiated polyether polyol isutilized in an amount of 5 to 40%, such as 5 to 20% by weight or 5 to15% by weight, based upon the total weight of the polyol blend.

In certain implementations, the aromatic polyester polyol and thealkanolamine-initiated polyether polyol are present in the polyol blendin a weight ratio of at least 2:1, such as 2:1 to 8:1, or, in some cases3:1 to 6:1 or 4:1 to 5:1. In certain implementations, thesaccharide-initiated polyether polyol and the alkanolamine-initiatedpolyether polyol are present in the polyol blend in a weight ratio of atleast 0.5:1, such as 0.5:1 to 4:1, or, in some cases 1:1 to 2:1 or 1:1to 1.5:1.

It was discovered, surprisingly, that inclusion of thealkanolamine-initiated polyether polyol in the polyol blends describedin this specification enabled the production of rigid PUR-PIR foams witha good combination of physical properties, even while limiting theamount of HCFO and tertiary amine blow catalyst used, thereby limitingtheir negative cost impact, while providing an isocyanate-reactivecomposition for use in producing such foams that has a long shelf life.

If desired, the polyol blend may include additional compounds thatcontain isocyanate-reactive groups, such as chain extenders and/orcrosslinking agents, and higher molecular weight polyether polyols andpolyester polyols not described above. Chain extenders and/orcrosslinking agents include, for example, ethylene glycol, propyleneglycol, butylene glycol, glycerol, diethylene glycol, dipropyleneglycol, dibutylene glycol, trimethylolpropane, pentaerythritol, ethylenediamine, diethyltoluenediamine, etc. Polyester polyols may be preparedfrom, for example, an organic dicarboxylic acid having 2 to 12 carbonatoms, such as an aliphatic dicarboxylic acid having 4 to 6 carbonatoms, and a polyvalent alcohol, such as a diol or triol having 2 to 12carbon atoms. Examples of the dicarboxylic acid are succinic acid,glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid,decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid,isophthalic acid and terephthalic acid. Instead of a free dicarboxylicacid, a corresponding dicarboxylic acid derivative such as adicarboxylic acid monoester or diester prepared by esterification withan alcohol having 1 to 4 carbon atoms or dicarboxylic anhydride can beused.

In certain implementations, the polyol blend has a weighted averagefunctionality of from 2 to 4, such as 2 to 3 or 2.5 to 3.0, and/or aweighted average hydroxyl number of from 300 to 500 mg KOH/g, such as300 to 400 mg KOH/g.

In certain implementations, the polyol blend comprises less than 20% byweight, less than 10% by weight, less than 5% by weight, or, in somecases, less than 1% by weight, of ethylene oxide, based on the totalweight of the saccharide initiated polyether polyol and thealkanolamine-initiated polyether polyol in the polyol blend.

As indicated, the isocyanate-reactive composition of this specificationfurther comprises a blowing agent composition. The blowing agentcomposition comprises: (1) a physical blowing agent comprising an HCFO;and (2) a carbon dioxide generating chemical blowing agent.

Suitable HCFOs include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd, Eand/or Z isomers), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf),HCFO1223, 1,2-dichloro-1,2-difluoroethene (E and/or Z isomers),3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene-2 (Eand/or Z isomers), 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and/orZ isomers). In some implementations, the boiling point, at atmosphericpressure, of the HCFO is at least −25° C., at least −20° C., or, in somecases, at least −19° C., and 40° C. or less, such as 35° C. or less, or,in some cases 33° C. or less. The HCFO may have a boiling point, atatmospheric pressure, of, for example, −25° C. to 40° C., or −20° C. to35° C., or −19° C. to 33° C.

In some implementations, the HCFO is utilized in an amount of at least10% by weight, such as 10 to 30% by weight or 10 to 20% by weight, basedon the total weight of the isocyanate-reactive composition.

In certain implementations, the isocyanate-reactive compositioncomprises one or more other physical blowing agents, such as otherhalogenated blowing agents, such as CFCs, HCFCs, and/or HFCs and/orhydrocarbon blowing agents, such as butane, n-pentane, cyclopentane,hexane, and/or isopentane (i.e. 2-methylbutane), etc. In otherembodiments, the isocyanate-reactive composition is substantially or, insome cases, completely free, of other physical blowing agents, such asother halogenated blowing agents, such as CFCs, HCFCs, and/or HFCsand/or hydrocarbon blowing agents, such as butane, n-pentane,cyclopentane, hexane, and/or isopentane (i.e. 2-methylbutane). As usedherein, the term “substantially free” when used with reference to theseblowing agents, means that the blowing agent is present, if at all, inan amount of less than 10% by weight, such as less than 1% by weight,based on the total weight of the blowing agent composition.

As indicated above, the isocyanate-reactive composition comprises acarbon dioxide generating chemical blowing agent, such as water and/orformate-blocked amines. In some of these implementations, the carbondioxide generating chemical blowing agent, such as water, is utilized inan amount of from 0.5 to 5.0% by weight, such as 1 to 4% by weight, or1.0 to 3.0% by weight, or 2.0 to 3.0% by weight, based on the totalweight of the isocyanate-reactive composition.

In certain implementations, the blowing agent composition comprises HCFOand a carbon dioxide generating chemical blowing agent, such as water,wherein the HCFO and the carbon dioxide generating chemical blowingagent are present in an amount of at least 90% by weight, such as atleast 95% by weight, or, in some cases, at least 99% by weight, based onthe total weight of the blowing agent composition. In certainimplementations, the HCFO and a carbon dioxide generating chemicalblowing agent are present in the blowing agent composition at a weightratio of at least 2:1, such as at least 4:1, such as 4:1 to 10:1 or 4:1to 6:1.

If desired, the blowing agent composition may include other physicalblowing agents, such as (a) other hydrofluoroolefins (HFOs), such aspentafluoropropane, tetrafluoropropene, 2,3,3,3-tetrafluoropropene,1,2,3,3-tetrafluoropropene, trifluoropropene, tetrafluorobutene,pentafluorobutene, hexafluorobutene, heptafluorobutene,heptafluoropentene, octafluoropentene, and nonafluoropentene; (b)hydrofluorocarbons (c) hydrocarbons, such as any of the pentane isomersand butane isomers; (d) hydrofluoroethers (HFEs); (e) C₁ to C₅ alcohols,C₁ to C₄ aldehydes, C₁ to C₄ ketones, C₁ to C₄ ethers and diethers andcarbon dioxide. Specific examples of such blowing agents are describedin United States Patent Application Publication No. US 2014/0371338 A1at [0051] and [0053], the cited portion of which being incorporatedherein by reference.

In some implementations, the isocyanate-reactive composition alsocomprises a surfactant. Any suitable surfactant can be used, includingorganosilicon compounds, such as polysiloxane-polyalkyene-blockcopolymers, such as a polyether-modified polysiloxane. Other usefulsurfactants include polyethylene glycol ethers of long chain alcohols,tertiary amine or alkanolamine salts of long chain alkyl acid sulfateesters, alkylsulfonic esters, or alkylarylsulfonic acids. Suchsurfactants are employed in amounts sufficient to stabilize the foamingreaction mixture against collapse and the formation of large and unevencells. In some implementations, surfactant is utilized in an amount of0.2 to 5.0% by weight, such as 1 to 3% by weight, based on the totalweight of the isocyanate-reactive composition.

As indicated earlier, the isocyanate-reactive composition furthercomprises a tertiary amine catalyst. As will be appreciated, tertiaryamine catalysts are known as “blow catalysts” since they have a greatereffect on the water-polyisocyanate blowing reaction. In someimplementations, tertiary amine catalyst comprises a morpholine and/oran imidazole. Suitable morpholine catalysts include, for example,dimorpholinodiethylether, dimorpholinodimethylether, N-ethylmorpholine,and N-methylmorpholine. Suitable imidazole catalysts include, forexample, imidazole, n-methylimidazole, and 1,2-dimethylimidazole.

In some implementations of the isocyanate-reactive compositions of thisspecification, however, the tertiary amine catalyst can be used in arelatively low amounts while still achieve the desired level ofreactivity of the water-polyisocyanate blowing reaction. For example, insome implementations, the tertiary amine catalyst, such as themorpholine and/or imidazole, is present in an amount of less than 2% byweight, such as 0.1 to 1.9% by weight, or 0.5 to 1.5% by weight based onthe total weight of the isocyanate-reactive composition.

Moreover, in some implementations, the isocyanate-reactive compositioncan be substantially or, in some cases, completely free of gel catalyst,such as organometallic catalysts (for example dibutyltin dilaurate,dibutyltin diacetate, stannous octoate, potassium octoate, potassiumacetate, and potassium lactate) that catalyze the reaction between apolyol and a polyisocyanate. As used herein, the term “substantiallyfree”, when used with reference to the absence of a catalyst, means thatthe catalyst is present in an amount of no more than 0.1% by weight,based on the total weight of the isocyanate-reactive composition.

In certain implementations, the isocyanate-reactive composition furthercomprises a trimerization catalyst, which is not an amine catalyst. Aswill be appreciated, a trimerization catalyst is a material thatcatalyzes the formation of isocyanurate groups from polyisocyanates.This means that isocyanates can react with one another to formmacromolecules with isocyanurate structures (polyisocyanurates). Thereactions between isocyanates and polyols to form urethanes andisocyanates and isocyanates (homopolymerization) to form isocyanuratescan occur at the same time or one after the other to form macromoleculeswith urethanes and isocyanurates.

Various trimerization catalysts may be suitable. In someimplementations, however, the trimerization catalyst comprises aquaternary ammonium salt, such as a quaternary ammonium carboxylate.Useful quaternary ammonium carboxylates include, for example,(2-hydroxypropyl)trimethylammonium 2-ethylhexanoate (Dabco® TMR fromEvonik Industries) and (2-hydroxypropyl)trimethylammonium formate(Dabco® TMR-2 from Evonik Industries). In some implementations, thetrimerization catalyst is present in the isocyanate-reactive compositionin an amount of from 0.25 to 3.0% by weight, such as 0.25 to 1% byweight, based on the total weight of the isocyanate-reactivecomposition.

Additional materials which may optionally be included in thefoam-forming compositions of the present invention include: pigments,colorants, fillers, antioxidants, flame retardants, and stabilizers.Exemplary flame retardants useful in the foam-forming composition of thepresent invention include, but are not limited to, reactive brominebased compounds known to be used in polyurethane chemistry andchlorinated phosphate esters, including but not limited to,tri(2-chloroethyl)phosphate (TECP), tri(1,3-dichloro-2-propyl)phosphate,tri(1-chloro-2-propyl)phosphate (TCPP) and dimethyl propyl phosphate(DMPP).

This specification is also directed to processes for producing rigidpolyurethane-polyisocyanurate (“PUR-PIR”) foams. In such processes, adiisocyanate and/or polyisocyanate (collectively “polyisocyanate”) isreacted with an isocyanate-reactive composition of the type describedabove. In some implementations, the isocyanate functional component andthe isocyanate-reactive composition are mixed at an isocyanate index offrom 90 to 150, such as 120 to 150.

In certain implementations, the polyol blend of the isocyanate-reactivecomposition is reacted with an polyisocyanate in the presence of theblowing agent composition, the catalyst composition, a surfactant andany other optional ingredients. The rigid foams may be prepared byblending all of the components of the isocyanate reactive compositiontogether in a phase stable mixture, and then mixing this in the properratio with the polyisocyanate. Alternatively, one or more of thecomponents, such as the surfactant, may be combined with thepolyisocyanate prior to mixing it with the isocyanate reactivecomponent. Other possible implementations would include adding one ormore of the components as a separate stream, together with theisocyanate reactive component and polyisocyanate. As used herein, theterm phase stable means that the isocyanate-reactive composition willnot separate when stored for 7 days at about 70° F. (or 21° C.).

Many foam machines are designed to condition and mix only two componentsin the proper ratio. For use of these machines, a premix of all thecomponents except the polyisocyanate can be advantageously employed.According to the two-component method (component A: polyisocyanate; andcomponent B: isocyanate-reactive composition which typically includesthe polyol blend, blowing agent, water, catalyst and surfactant), thecomponents may be mixed in the proper ratio at a temperature of 5 to 50°C., such as 15 to 35° C., injected or poured into a mold having thetemperature controlled to within a range of from 20 to 70° C., such as35 to 60° C. The mixture then expands to fill the cavity with the rigidpolyurethane foam. This simplifies the metering and mixing of thereacting components which form the foam-forming mixture, but requiresthat the isocyanate reactive composition be phase stable.

Alternatively, the rigid polyurethane foams may also be prepared by theso-called “quasi prepolymer” method. In this method, a portion of thepolyol component is reacted in the absence of the urethane-formingcatalysts with the polyisocyanate component in proportion so as toprovide from 10 percent to 35 percent of free isocyanate groups in thereaction product based on the prepolymer. To prepare foam, the remainingportion of the polyol is added and the components are allowed to reacttogether in the presence of the blowing agent and other appropriateadditives such as the catalysts, and surfactants. Other additives may beadded to either the isocyanate prepolymer or remaining polyol or bothprior to the mixing of the components, whereby at the end of thereaction, rigid foam is provided.

Furthermore, the rigid foam can be prepared in a batch or continuousprocess by the one-shot or quasi-prepolymer methods using any well-knownfoaming apparatus. The rigid foam may be produced in the form of slabstock, moldings, cavity fillings, sprayed foam, frothed foam orlaminates with other materials such as hardboard, plasterboard,plastics, paper or metal as facer substrates.

For closed-cell insulating foams, the object is to retain the blowingagent in the cells to maintain a low thermal conductivity of theinsulating material, i.e., the rigid foam. Thus, high closed-cellcontent in the foam is desirable. Foams produced according toimplementations of the present specification have more than 80 percent,typically more than 85 percent, or more than 88 percent closed-cellcontent as measured according to ASTM D6226-15. Furthermore, the thermalconductivity of foams produced according to various implementations ofthe present specification indicates that the foams have acceptableinsulating properties, i.e., the foams have a thermal conductivitymeasured at 35° F. (2° C.) of less than 0.132 BTU-in/h-ft²-° F. andmeasured at 75° F. (24° C.) of less than 0.149 BTU-in/h-ft²-° F. forfoam from the core of 2-inch thick panels, as measured according to ASTMC518-15.

This specification also relates to the use of the rigid foams describedherein for thermal insulation. That is, the rigid foams of the presentspecification may find use as an insulating material in refrigerationapparatuses since the combination of good thermal insulation and otherproperties described herein is particularly appropriate here. The rigidfoams according to the invention can be used, for example, as anintermediate layer in composite elements or for filling hollow spaces ofrefrigerators and freezers, or refrigerated trailers. The inventivefoams may also find use in the construction industry or for thermalinsulation of long-distance heating pipes and containers.

As such, the present invention also provides a composite articlecomprising rigid foam as disclosed herein sandwiched between one or morefacer substrates. In certain implementations, the facer substrate may beplastic (such a polypropylene resin reinforced with continuousbi-directional glass fibers or a fiberglass reinforced polyestercopolymer), paper, wood, or metal. For example, in certainimplementations, the composite article may be a refrigeration apparatussuch as a refrigerator, freezer, or cooler with an exterior metal shelland interior plastic liner. In certain implementations, therefrigeration apparatus may be a trailer, and the composite article mayinclude the foams produced according to the present invention insandwich composites for trailer floors.

It has been found, surprisingly, that the particular isocyanate-reactivecompositions described herein can be particularly suitable for use indiscontinuous open pour applications, such as is often used in theproduction of discontinuous panels or doors, such as garage doors. Aswill be appreciated, in such a discontinuous process, the reactionmixture (the mixture of the isocyanate-reactive component and theisocyanate-functional component) is poured into a cavity of a mold ofthe desired part, in which the cavity is lined with a facer, which canbe a metal sheet, particle board, plaster board, fiber cement, or aplastic. The foam adheres to the facers as it reacts and cures. Theresulting faced panel is then removed from the cavity. To be effectivelyused in such a process, the reaction mixture must exhibit the rightlevel of reactivity (sufficient to allow for adequate flow of themixture) resulting from an ideal balance of blow and gel reactivity. Asa result, certain implementations of the present invention are directedto the use of the reaction mixtures described herein in such a process.

It has been discovered that isocyanate-reactive components describedherein, and the rigid foams produced therefrom, can exhibit aparticularly desirable combination of properties. First, the rigid foamscan have a thermal conductivity measured at 75° F. (24° C.) of less than0.149 BTU-in/h-ft²-° F. as measured according to ASTM C518-15 at a corefoam density of 1.8 to 2.0 lb/ft′ (28.8 to 32.0 kg/m³). Second, theisocyanate-reactive composition is phase stable and has a long shelflife. Here, when it is stated that the isocyanate-reactive compositionhas a “long” shelf life it means that after storing theisocyanate-reactive composition for 15 days (360 hours) at 60° C., whenthe isocyanate-reactive composition is combined with the polyisocyanate,both (a) the cream and gel times of the foam produced thereby remainswithin 10% of the initial cream and gel times (the cream and gel timesof such a foam if produced immediately and not after storing theisocyanate-reactive composition for 15 days (360 hours) at 60° C.) and(b) the free rise density foam produced thereby remains within 10% ofthe initial free rise density (the free rise density of such a foam isproduced immediately and not after storing the isocyanate-reactioncomposition for 15 days (360 hours) at 60° C.), even in cases where theisocyanate-reactive composition comprises 2.5-3% by weight of water and9-13% by weight HCFO, based on the total weight of theisocyanate-reactive composition. In some cases, this initial gel time is76 seconds, ±5 seconds, which can be ideally suited for certaindiscontinuous panel applications. Third, it was determined that thecream and gel times and density for the foams could match that of asimilar comparative formulation utilizing a hydrofluorocarbon blowingagent (HFC245fa).

Various aspects of the subject matter described herein are set out inthe following numbered clauses:

Clause 1. An isocyanate-reactive composition, comprising: (a) a polyolblend comprising: (1) a saccharide-initiated polyether polyol having anOH number of from 200 to 600 mg KOH/g and a functionality of 4 to 6; (2)an aromatic polyester polyol having an OH number of 150 to 410 mg KOH/gand a functionality of 1.5 to 3; and (3) an alkanolamine-initiatedpolyether polyol having an OH number of at least 500 mg KOH/g and afunctionality of 2.5 to 4; (b) a blowing agent composition comprising:(1) a hydrochlorofluoroolefin; and (2) a carbon dioxide generatingchemical blowing agent; and (c) a tertiary amine catalyst.

Clause 2. The isocyanate-reactive composition of clause 1, wherein thesaccharide-initiated polyether polyol is the reaction product of atleast one alkylene oxide with one or more starter compounds in thepresence of a suitable catalyst, in which the starter compound comprisessucrose, such as where the saccharide, such as sucrose, is reacted withpropylene oxide.

Clause 3. The isocyanate-reactive composition of one of clause 1 orclause 2, wherein the saccharide-initiated polyether polyol has anaverage molecular weight of 300 to 1600 Da, such as 440 to 1000 Da.

Clause 4. The isocyanate-reactive composition of one of clause 1 toclause 3, wherein the saccharide initiated polyether polyol has an OHnumber of 300 to 550 mg KOH/g, 400 to 500 mg KOH/g, or 450 to 500 mgKOH/g.

Clause 5. The isocyanate-reactive composition of one of clause 1 toclause 4, wherein the saccharide-initiated polyether polyol has afunctionality of 5 to 6, 5.2 to 5.8, or 5.4 to 5.6.

Clause 6. The isocyanate-reactive composition of one of clause 1 toclause 5, wherein the saccharide-initiated polyether polyol is presentin an amount of 10 to 45% by weight, 10 to 30% by weight, or 15 to 25%by weight, based on the total weight of the polyol blend.

Clause 7. The isocyanate-reactive composition of one of clause 1 toclause 6, wherein the aromatic polyester polyol is the reaction productof a glycol and/or triol comprising ethylene glycol, propylene glycol,butylene glycol, 1,3-butanediol, neopentyl glycol, diethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol,trimethylolethane, trimethyolpropane, pentanediol, hexanediol,heptanediol, 1,3- and 1,4-dimethylol cyclohexane, or a mixture of anytwo or more thereof, with an aromatic diacid or aromatic anhydridecomprising phthalic acid, isophthalic acid, terephthalic acid, orphthalic anhydride, or a mixture of any two or more thereof.

Clause 8. The isocyanate-reactive composition of one of clause 1 toclause 7, wherein the aromatic polyester polyol has an OH number of 150to 360 mg KOH/g, 200 to 335 mg KOH/g, or 200 to 250 mg KOH/g.

Clause 9. The isocyanate-reactive composition of one of clause 1 toclause 8, wherein the aromatic polyester polyol has a functionality of1.9 to 2.5.

Clause 10. The isocyanate-reactive composition of one of clause 1 toclause 9, wherein the aromatic polyester polyol is present in an amountof 50 to 85% by weight or 60 to 80% by weight, based upon the totalweight of the polyol blend.

Clause 11. The isocyanate-reactive composition of one of clause 1 toclause 10, wherein the aromatic polyester polyol and thesaccharide-initiated polyether polyol are present in the polyol blend ina weight ratio of at least 2:1, 2:1 to 8:1, 2:1 to 6:1, or 3:1 to 4:1.

Clause 12. The isocyanate-reactive composition of one of clause 1 toclause 11, wherein the alkanolamine used to prepare thealkanolamine-initiated polyether polyol comprises monoethanolamine,1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol,1-(2-aminoethoxy) ethanol, 1-amino-2-butanol, 2-amino-3-butanol,2-amino-2-methylpropanol, 5-amino pentanol, 3-amino-2, 2-dimethylpropanol, 4-aminocyclohexanol, or a mixture of any two or more thereof,wherein the alkanolamine is reacted with an alkylene oxide comprisingethylene oxide, propylene oxide, butylene oxide, styrene oxide,epichlorohydrin, or a mixture of any two or more thereof.

Clause 13. The isocyanate-reactive composition of one of clause 1 toclause 12, wherein the alkanolamine-initiated polyether polyol has an OHnumber of 500 to 900 mg KOH/g, 600 to 800 mg KOH/g, or 680 to 720 mgKOH/g.

Clause 14. The isocyanate-reactive composition of one of clause 1 toclause 13, wherein the alkanolamine-initiated polyether polyol has afunctionality of 2.5 to 3.5.

Clause 15. The isocyanate-reactive composition of one of clause 1 toclause 14, wherein the alkanolamine-initiated polyether polyol ispresent in an amount of 5 to 40% by weight, 5 to 20% by weight or 5 to15% by weight, based upon the total weight of the polyol blend.

Clause 16. The isocyanate-reactive composition of one of clause 1 toclause 15, wherein the aromatic polyester polyol and thealkanolamine-initiated polyether polyol are present in the polyol blendin a weight ratio of at least 2:1, 2:1 to 8:1, 3:1 to 6:1, or 4:1 to5:1.

Clause 17. The isocyanate-reactive composition of one of clause 1 toclause 16, wherein the saccharide-initiated polyether polyol and thealkanolamine-initiated polyether polyol are present in the polyol blendin a weight ratio of at least 0.5:1, 0.5:1 to 4:1, 1:1 to 2:1, or 1:1 to1.5:1.

Clause 18. The isocyanate-reactive composition of one of clause 1 toclause 17, wherein the polyol blend has a weighted average functionalityof 2 to 4, 2 to 3, or 2.5 to 3.0.

Clause 19. The isocyanate-reactive composition of one of clause 1 toclause 18, wherein the polyol blend has a weighted average hydroxylnumber of 300 to 500 mg KOH/g or 300 to 400 mg KOH/g.

Clause 20. The isocyanate-reactive composition of one of clause 1 toclause 19, wherein the polyol blend comprises less than 20% by weight,less than 10% by weight, less than 5% by weight, or less than 1% byweight, of ethylene oxide, based on the total weight of the saccharideinitiated polyether polyol and the alkanolamine-initiated polyetherpolyol in the polyol blend.

Clause 21. The isocyanate-reactive composition of one of clause 1 toclause 20, wherein the HCFO comprises 1-chloro-3,3,3-trifluoropropene(HCFO-1233zd, E and/or Z isomers), 2-chloro-3,3,3-trifluoropropene(HCFO-1233xf), HCFO1223, 1,2-dichloro-1,2-difluoroethene (E and/or Zisomers), 3,3-dichloro-3-fluoropropene,2-chloro-1,1,1,4,4,4-hexafluorobutene-2 (E and/or Z isomers),2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and/or Z isomers), or amixture of any two or more thereof.

Clause 22. The isocyanate-reactive composition of one of clause 1 toclause 21, wherein the HCFO is present in an amount of at least 10% byweight, 10 to 30% by weight or 10 to 20% by weight, based on the totalweight of the isocyanate-reactive composition.

Clause 23. The isocyanate-reactive composition of one of clause 1 toclause 22, wherein the isocyanate-reactive composition comprises one ormore CFCs, HCFCs, and/or HFCs, and/or one or more hydrocarbon blowingagents comprising butane, n-pentane, cyclopentane, hexane, and/orisopentane.

Clause 24. The isocyanate-reactive composition of one of clause 1 toclause 23, wherein the isocyanate-reactive composition is substantiallyor, in some cases, completely free, of CFCs, HCFCs, and/or HFCs and/orbutane, n-pentane, cyclopentane, hexane, and/or isopentane.

Clause 25. The isocyanate-reactive composition of one of clause 1 toclause 24, wherein the carbon dioxide generating chemical blowing agentcomprises water that is present in an amount of 0.5 to 5.0% by weight, 1to 4% by weight, 1.0 to 3.0% by weight, or 2.0 to 3.0% by weight, basedon the total weight of the isocyanate-reactive composition.

Clause 26. The isocyanate-reactive composition of one of clause 1 toclause 25, wherein the HCFO and the carbon dioxide generating chemicalblowing agent are present in an amount of at least 90% by weight, atleast 95% by weight, or at least 99% by weight, based on the totalweight of the blowing agent composition.

Clause 27. The isocyanate-reactive composition of one of clause 1 toclause 26, wherein the HCFO and a carbon dioxide generating chemicalblowing agent are present in the blowing agent composition at a weightratio of at least 2:1, at least 4:1, 4:1 to 10:1 or 4:1 to 6:1.

Clause 28. The isocyanate-reactive composition of one of clause 1 toclause 27, wherein the isocyanate-reactive composition further comprisesa surfactant comprising an organosilicon compound, such as apolysiloxane-polyalkyene-block copolymer (such as a polyether-modifiedpolysiloxane), a polyethylene glycol ether of a long chain alcohol, atertiary amine or an alkanolamine salt of a long chain alkyl acidsulfate ester, an alkylsulfonic ester, or an alkylarylsulfonic acid.

Clause 29. The isocyanate-reactive composition of one of clause 1 toclause 28, wherein the tertiary amine catalyst comprises a morpholineand/or an imidazole, such as where the morpholine catalyst comprisesdimorpholinodiethylether, dimorpholinodimethylether, N-ethylmorpholine,N-methylmorpholine, or a mixture of any two or more thereof, and/or theimidazole catalyst comprises imidazole, n-methylimidazole,1,2-dimethylimidazole, or a mixture of any two or more thereof.

Clause 30. The isocyanate-reactive composition of one of clause 1 toclause 29, wherein the tertiary amine catalyst is present in an amountof less than 2% by weight, 0.1 to 1.9% by weight, or 0.5 to 1.5% byweight, based on the total weight of the isocyanate-reactivecomposition.

Clause 31. The isocyanate-reactive composition of one of clause 1 toclause 30, wherein the isocyanate-reactive composition is substantiallyor, in some cases, completely free of gel catalyst, such asorganometallic catalysts (for example dibutyltin dilaurate, dibutyltindiacetate, stannous octoate, potassium octoate, potassium acetate, andpotassium lactate).

Clause 32. The isocyanate-reactive composition of one of clause 1 toclause 31, wherein the isocyanate-reactive composition further comprisesa trimerization catalyst, such as a quaternary ammonium salt, such as aquaternary ammonium carboxylate, such as(2-hydroxypropyl)trimethylammonium 2-ethylhexanoate and/or(2-hydroxypropyl)trimethylammonium formate.

Clause 33. The isocyanate-reactive composition of clause 32, wherein thetrimerization catalyst is present in the isocyanate-reactive compositionin an amount of 0.25 to 3.0% by weight or 0.25 to 1% by weight, based onthe total weight of the isocyanate-reactive composition.

Clause 34. A process for producing rigid PUR-PIR foam comprising mixingan organic isocyanate with the isocyanate-reactive composition of one ofclause 1 to claim 33 at an isocyanate index of from 90 to 150 or 120 to150 to form a reaction mixture.

Clause 35. The process of clause 34, wherein the organic isocyanatecomprises a methylene-bridged polyphenyl polyisocyanate and/or aprepolymer of methylene-bridged polyphenyl polyisocyanate having anaverage functionality of 1.8 to 3.5 or 2.0 to 3.1, isocyanate moietiesper molecule, and an NCO content of 25 to 32 weight percent.

Clause 36. The process of clause 34 or clause 35, wherein the reactionmixture is poured into a cavity of a mold of a desired part, wherein thecavity is lined with a facer.

Clause 37. A composite article comprising rigid PUR-PIR produced by theprocess of one of clause 34 to clause 36 sandwiched between one or morefacer substrates.

Clause 38. The composite article of clause 37, wherein the facersubstrate comprises a metal sheet, particle board, plaster board, fibercement, or a plastic.

Clause 39. The composite article of clause 37 or clause 38, wherein thecomposite article is embodied as a door, such as a garage door.

The non-limiting and non-exhaustive examples that follow are intended tofurther describe various non-limiting and non-exhaustive implementationswithout restricting the scope of the implementations described in thisspecification.

EXAMPLES Example 1

Foam-forming compositions were prepared using the ingredients andamounts (in parts by weight) set forth in Table 1. The followingmaterials were used:

POLYOL 1: an aromatic polyester polyol having an OH number of 225 to 245mg KOH/g and a functionality of 2, commercially available from Invistaas Terate® HT 5500.

POLYOL 2: a sucrose and propylene glycol-initiated polyether polyolhaving an OH number of about 470 mg KOH/g and a functionality of about5.2, prepared by propoxylating a mixture of sucrose and water;

POLYOL 3: a monoethanolamine-initiated polyether polyol having an OHnumber of 685 to 715, a functionality of 3, and a nitrogen content of5.8% by weight, prepared by propoxylating monoethanolamine.

POLYOL 4: an ethylenediamine-initiated polyether polyol having an OHnumber of 600 to 660, a functionality of 4, and a nitrogen content of7.8% by weight, prepared by propoxylating ethylenediamine.

POLYOL 5: a triethanolamine-initiated polyether polyol having an OHnumber of 140 to 160, a functionality of 3, and a nitrogen content of1.3% by weight, prepared by propoxylating triethanolamine.

POLYOL 6: a monoethanolamine-initiated polyether polyol having an OHnumber of 340 to 360, a functionality of 3, and a nitrogen content of2.9% by weight, prepared by propoxylating monoethanolamine.

SURFACTANT: a non-hydrolysable polyether polydimethylsiloxane copolymercommercially available from Evonik Industries under the trade nameTegostab® B 8465.

CATALYST A: (2-hydroxypropyl)trimethylammonium formate commerciallyavailable as Dabco® TMR-2 from Evonik Industries;

CATALYST B: 2,2′-dimorpholinodiethylether (JEFFCAT® DMDEE fromHuntsman);

FLAME RETARDANT A: a reactive bromine-containing diester/ether diol oftetrabromophthalic anhydride commercially available from AlbemarleCorporation as Saytex® RB-79

FLAME RETARDANT B: alkyl phosphate flame retardant based onTris(2-chloroisopropyl) phosphate commercially available from ICLIndustrial Products as Fyrol® PCF

HCFO 1233zd(E): trans-1,1,1-trifluoro-3-chloropropene, ahydrochlorofluoro olefin blowing agent which has a boiling point of 19°C. that is commercially available from Honeywell International Inc. asSolstice® LBA;

ISOCYANATE: a high functionality polymeric diphenylmethane diisocyanate(PMDI) with a NCO content of 30.0 to 31.4% and a viscosity of 610 to 790centipoise at 25° C.

In each case, a master batch was prepared by mixing the polyols,catalysts, surfactant, water and blowing agents in the amounts indicatedin Table 1. Foams were prepared by mixing the masterbatch with theamount of isocyanate indicated in Table 1 and pouring the mixture intoan 83 ounce paper cup. The cream time, gel time, tack-free time and freerise density (“1-RD”) were recorded. Foams were prepared after initiallypreparing the master batch and also after aging the master batches forvarious amounts of time list in Table 2 at 60° C. to assess shelf life.Results are set forth in Table 2 (reported results represent the averageresults of three replicate experiments). Flow was evaluated as describedin U.S. Pat. No. 10,106,641 B2 (at col. 12, lines 22-61, the citedportion of which being incorporated herein by reference) and the resultsare set forth in Table 3. Additionally, a pressure transducer waslocated 10 cm above the protruding sheet metal based edge, whichrecorded the foaming pressure during the process. The rise rate wasderived from the foam height data as a function of time. Example 1 is aninventive example.

TABLE 1 Material 1 2 3 4 POLYOL 1 42.8 42.8 42.8 42.8 POLYOL 2 13 13 1313 POLYOL 3 9 — — — POLYOL 4 — 9 — — POLYOL 5 — — 9 — POLYOL 6 — — — 9SURFACTANT 2.25 2.25 2.25 2.25 CATALYST A 0.45 0.45 0.45 0.45 CATALYST B1 1 1 1 FLAME RETARDANT A 3 3 3 3 FLAME RETARDANT B 13 13 13 13 Water2.5 2.5 2.5 2.5 HCFO 1233zd(E) 13 13 13 13 Total 100 100 100 100ISOCYANATE 125 125 125 125

TABLE 2 Example Aging Time Reactivity (s) Formulation (days) Cream GelTack-Free FRD (pcf) Formulation 1 0 20 116 177 1.78 6 19 116 199 1.89 1519 120 193 1.89 Formulation 2 0 19 97 135 1.79 6 19 103 163 1.87 15 1897 150 1.91 Formulation 3 0 20 135 197 1.76 6 19 139 246 1.95 15 19 140247 1.93 Formulation 4 0 20 136 256 1.79 6 21 138 248 1.85 15 22 147 2351.89

TABLE 3 Aging Final Max. Example Time Height Pressure Max RiseFormulation (days) (cm) (hPa) Rate (cm/s) Formulation 1 0 104 152 1.1915 106 142 1.16 Formulation 2 0 102 188 1.40 15 102 177 1.43 Formulation3 0 107 88 1.10 15 113 61 1.12 Formulation 4 0 115 86 1.12 15 110 781.03

As is apparent, formulations 1-4 displayed minimal changes to the creamtime (5%) while larger differences in gel time were observed (Table 2)after aging. Formulation 1 and 3 afforded excellent shelf-life with anet increase of 3.4 and 3.2%, respectively, after 15 days of agingwhereas formulations 2 and 4 displayed larger increases in gel time of6.5 and 8%, respectively. While all of these values are within the 10%shelf-life window, formulation 2 resulted in an initial gel timedecrease of 10 seconds (relative to formulation 1) while formulations 3and 4 resulted in initial gel time increases (relative to formulation 1)of 19-20 seconds, respectively. Such a shift in gel times can beundesirable based on the manufacturing equipment and process requirementused to produce discontinuous foam panels. Balancing of the gel time isfurther complicated by the necessity to incorporate a certain amount oftrimerization catalyst in order to achieve the required flameretardance. Formulation 1 exhibited ideal flow properties (high riserate and final height) while formulation 2 exhibits a lower final heighteven though the max rise rate was higher (believed to be due to the muchfaster gel time) (Table 3). While formulations 3 and 4 afforded higherfinal heights, the rise rates were lower and thus the final heights arebelieved to be an artifact of the greatly elongated gel times.

Although the invention has been described in detail in the foregoing forthe purpose of illustration, it is to be understood that such detail issolely for that purpose and that variations can be made therein by thoseskilled in the art without departing from the spirit and scope of theinvention except as it may be limited by the claims.

What is claimed is:
 1. An isocyanate-reactive composition comprising: (a) a polyol blend comprising: (1) a saccharide-initiated polyether polyol having an OH number of from 200 to 600 mg KOH/g and a functionality of 4 to 6; (2) an aromatic polyester polyol having an OH number of 150 to 410 mg KOH/g and a functionality of 1.5 to 3; and (3) an alkanolamine-initiated polyether polyol having an OH number of at least 500 mg KOH/g and a functionality of 2.5 to 4; (b) a blowing agent composition comprising: (1) a hydrochlorofluoroolefin; and (2) a carbon dioxide generating chemical blowing agent; and (c) a tertiary amine catalyst.
 2. The isocyanate-reactive composition of claim 1, wherein the saccharide-initiated polyether polyol is present in an amount of 10 to 45% by weight, based on the total weight of the polyol blend.
 3. The isocyanate-reactive composition of claim 2, wherein the aromatic polyester polyol is present in an amount of 50 to 85% by weight, based on the total weight of the polyol blend.
 4. The isocyanate-reactive composition of claim 3, wherein the aromatic polyester polyol and the saccharide-initiated polyether polyol are present in the polyol blend in a weight ratio of 2:1 to 8:1.
 5. The isocyanate-reactive composition of claim 3, wherein the alkanolamine-initiated polyether polyol is present in an amount of 5 to 40% by weight, based on the total weight of the polyol blend.
 6. The isocyanate-reactive composition of claim 1, wherein the alkanolamine-initiated polyether polyol is a propoxylation reaction product of monoethanolamine.
 7. The isocyanate-reactive composition of claim 5, wherein the aromatic polyester polyol and the alkanolamine-initiated polyether polyol are present in the polyol blend in a weight ratio of 2:1 to 8:1.
 8. The isocyanate-reactive composition of claim 7, wherein the saccharide-initiated polyether polyol and the alkanolamine-initiated polyether polyol are present in the polyol blend in a weight ratio of 0.5:1 to 4:1.
 9. The isocyanate-reactive composition of claim 1, wherein the polyol blend has a weighted average functionality of 2.5 to 3.0 and a weighted average hydroxyl number of 300 to 400 mg KOH/g.
 10. The isocyanate-reactive composition of claim 1, wherein the hydrochlorofluoroolefin comprises 1-chloro-3,3,3-trifluoropropene.
 11. The isocyanate-reactive composition of claim 1, wherein the hydrochlorofluoroolefin is present in an amount of 10 to 30% by weight, based on the total weight of the isocyanate-reactive composition.
 12. The isocyanate-reactive composition of claim 1, wherein the isocyanate-reactive composition is substantially free of CFCs, HCFCs, HFCs and/or hydrocarbons.
 13. The isocyanate-reactive composition of claim 1, wherein the hydrochlorofluoroolefin and carbon dioxide generating chemical blowing agent are present in the blowing agent composition at a weight ratio of 4:1 to 10:1.
 14. The isocyanate-reactive composition of claim 1, wherein the tertiary amine catalyst comprises a morpholine and/or an imidazole.
 15. The isocyanate-reactive composition of claim 14, wherein the morpholine and/or imidazole is present in an amount of less than 3% by weight, based on the total weight of the isocyanate-reactive composition.
 16. The isocyanate-reactive composition of claim 1, wherein the isocyanate-reactive composition is substantially free of organometallic catalysts.
 17. The isocyanate-reactive composition of claim 1, further comprising a trimerization catalyst comprising a quaternary ammonium salt.
 18. A process for producing a rigid polyurethane-polyisocyanurate foam, comprising mixing an diisocyanate and/or polyisocyanate with the isocyanate-reactive composition of claim 1 at an isocyanate index of from 90 to 150 to form a reaction mixture.
 19. The process of claim 18, wherein the reaction mixture is poured into a cavity of a mold of a desired part, wherein the cavity is lined with a facer. 